CN103212484B - Phosphorite reverse flotation process - Google Patents
Phosphorite reverse flotation process Download PDFInfo
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- CN103212484B CN103212484B CN201310134970.6A CN201310134970A CN103212484B CN 103212484 B CN103212484 B CN 103212484B CN 201310134970 A CN201310134970 A CN 201310134970A CN 103212484 B CN103212484 B CN 103212484B
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Abstract
The invention relates to a phosphorite reverse flotation process which comprises the following steps: after carrying out ore crushing, ore grinding and size mixing on phosphorite, enabling the obtained product to enter the reverse flotation process, wherein ore pulp obtained after size mixing is added with sulfuric acid or phosphoric acid to form a regulator and an inhibitor and then is added with micromolecule organic acid to form a combined inhibitor for inhibiting phosphate minerals; carrying out reverse flotation to separate out carbonate minerals by using fatty acids or fatty acid soaps as a collecting agent so as to obtain high-grade low-magnesium phosphate concentrates. The phosphorite reverse flotation process has the following advantage that the micromolecule organic acid inhibitor is adopted to implement effective separation of collophanite and dolomite, so that the grade of the phosphate concentrates is improved, the grade of tailings is reduced and the recovery rate can be improved. Meanwhile, application of phosphoric acid and derivatives thereof to phosphorite reverse flotation is replaced, so that phosphorus resources are saved, service time of phosphate rock resources is prolonged and the defects in the prior art are overcome.
Description
Technical field
The present invention relates to a kind of phosphate reverse flotation technique.
Background technology
Phosphorus ore is the requisite basic material producing phosphate fertilizer, phosphorus chemical product.China's phosphate rock resource reserves 167.86 hundred million tons, average grade 16.95%, the high grade ore that can directly utilize only can maintain more than ten years exploitation, and mid-low grade collophanite ore due to various mineral inlay relation complexity, disseminated grain size is thin, dissociative is poor, the simultaneously feature such as carbonate mineral content, its exploitation belong to global problem.In phosphate reverse flotation, sulfuric acid and phosphoric acid are as the inhibitor of reverse flotation, and there is sulfuric acid, phosphoric acid consumption is large, inhibition is poor, selective low, makes beneficiation cost high.
Summary of the invention
Problem to be solved by this invention is a kind of phosphate reverse flotation technique proposed for above-mentioned existing technology, and it adopts sulfuric acid to combine as inhibitor with small molecular organic acid, and the inexpensive easy buying of its raw material, easy to use, inhibition is better.
The present invention for solving the problems of the technologies described above adopted technical scheme is: a kind of phosphate reverse flotation technique, it is characterized in that including following steps: rock phosphate in powder is entered reverse floatation process by muck, ore grinding with after sizing mixing, wherein, sulfuric acid or phosphoric acid is added in gained ore pulp as adjusting agent and inhibitor after sizing mixing, add small molecular organic acid again as combined depressant, suppress phosphate mineral; Adopt fatty acid or fatty acid soaps class collecting agent, carry out reverse flotation and deviate from carbonate mineral, obtain high-grade low magnesium phosphorus concentrate.
By such scheme, described reverse floatation process is direct reverse flotation technique, single reverse floatation process or bi-anti-symmetric matrix technique, to deviate from carbonate mineral, reduces the content of MgO.
By such scheme, described interpolation sulfuric acid or phosphoric acid are to adjust the pH value 4-6 of ore pulp.
By such scheme, described small molecular organic acid is the mixture of citric acid, succinic acid, malic acid, gallic acid and tannic acid any two kinds, and its consumption in reverse floatation process is 0.5kg/t ~ 3.0kg/t rock phosphate in powder.
By such scheme, the consumption of described fatty acid or fatty acid soaps class collecting agent is 0.3 ~ 2.0kg/t rock phosphate in powder.
The present invention has the following advantages: small molecular organic acid combined depressant uses, because they have wide material sources, well water-soluble, selective height, the features such as non-environmental-pollution, small molecular organic acid combined depressant affects floatation process mainly through three kinds of different action modes in floatation process, and (1) generates stable soluble chelating thing with activated metal ionization in ore pulp, thus prevent it to be adsorbed onto mineral surfaces, reach inhibitory action; (2) with mineral surfaces Action of Metal Ions, generate hydrophily product and be attached to mineral surfaces, and hinder the absorption of collecting agent, thus reach the object suppressing Phosphate minerals; (3) generate stable water miscible chelate with the ionization of mineral surfaces activated metal to be dissolved in ore pulp, thus reach mineral surfaces desactivation.Adopting small molecular organic acid inhibitor to realize effectively being separated of collophane and dolomite, being improve phosphorus concentrate grade, reducing the grade of mine tailing, can the rate of recovery be improved.Substitute phosphoric acid and the application of derivative in phosphate reverse flotation thereof simultaneously, thus save phosphor resource, extend the service time of phosphate rock resource, overcome the deficiencies in the prior art.
Accompanying drawing explanation
Fig. 1 is at the process chart of the application of the single reverse flotation of Yichang phosphate rock;
Fig. 2 is at the process chart of the application of the single reverse flotation of Guizhou phosphorus ore;
Fig. 3 is at the technique for applying flow chart of Sichuan phosphorus ore direct reverse flotation;
Fig. 4 is at the technique for applying flow chart of Yunnan Haikou phosphorus ore bi-anti-symmetric matrix.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described in detail.
Embodiment 1:
1) Yichang high-magnesium-phosphorus ore contains P
2o
528.54%, MgO6.03%, raw ore by crusher in crushing extremely-12mm, then carries out ore grinding by ore mill, and mog is-0.074mm80.45%, adds water and sizes mixing to concentration 20-50%, roughly selects first add H at reverse flotation
2sO
4consumption is 12kg/t raw ore, and the pH of adjustment ore pulp is 5.2-6, and rear interpolation citric acid and succinic acid are as combined depressant, and its quality proportioning is 2:1, and its consumption is 1.5kg/t raw ore, and the consumption of fatty acid anion type collecting agent TSM-2 is 0.4kg/t raw ore, scans H
2sO
4scan closed circuit flow test for carrying out reverse flotation one thick under 1kg/t raw ore condition, the flow chart of test, as Fig. 1, obtains concentrate P
2o
534.52%, productive rate 77.19%, the P2O5 rate of recovery is 97.71%.Adopt sulfuric acid, citric acid and succinic acid as combined depressant, when the rate of recovery is 3.0kg/t than sulfuric acid and phosphoric acid as inhibitor consumption, improve 3.78%, productive rate improves 4.01%, tailings grade reduces 3.16%, illustrate that citric acid and succinic acid effectively can suppress the flotation of phosphate mineral as combined depressant, improve the efficiency of separation.
Embodiment 2:
Guizhou phosphorus ore contains P
2o
5be 23.45%, the content of MgO is 3.54%.Raw ore by crusher in crushing, then carries out ore grinding by ore mill, and mog is-0.074mm84.00%, adds water and sizes mixing to concentration 20-50%, roughly selects first add H at reverse flotation
2sO
4consumption is 12.0kg/t raw ore, and rear interpolation succinic acid, malic acid are combined depressant, and its quality proportioning is 3:1, and its consumption is 1.5kg/t raw ore, then adds fatty acid anionic TSM-2 collecting agent, and consumption is 1.3kg/t raw ore, scans H
2sO
4scan closed circuit flow test for carrying out reverse flotation one thick under the condition of 3.0kg/t raw ore, the flow chart of test, as Fig. 2, obtains concentrate P
2o
530.25%, productive rate 65.67%, P
2o
5the rate of recovery is 84.71%.
Embodiment 3:
The multielement analysis of Sichuan phosphorus ore in table 1, table 1 phosphorus ore chemistry multielement analysis
| Element | P 2O 5 | MgO | CaO | SiO 2 | Fe 2O 3 | Al 2O 3 |
| Content/% | 17.71 | 6.81 | 30.89 | 21.80 | 5.48 | 3.18 |
Utilize normal temperature direct reverse flotation, the grade 17.71% of raw ore, raw ore passes through crusher in crushing, ore grinding is carried out again by ore mill, mog is-0.074mm91.8%, add water and size mixing to concentration 20-50%, direct flotation adopts one roughing once purging selection and primary cleaning operation, roughly select sodium carbonate, waterglass, fatty acid anion collecting agent TSM-2 consumption be respectively 6.0kg/t raw ore, 2.0kg/t raw ore, 1.0kg/t raw ore, the consumption of selected waterglass is 1.0kg/t raw ore, and the consumption scanning fatty acid anion collecting agent TSM-2 is 0.5kg/t raw ore; Reverse flotation adopts one thick two to sweep technique, roughly select the sulfuric acid 6.0kg/t raw ore of operation, citric acid and gallic acid (its quality proportioning is 4:1) as combined depressant consumption 1.0kg/t raw ore, fatty acid anion collecting agent TSM-2 consumption 0.45kg/t raw ore, sulfuric acid 6.0kg/t raw ore is with the addition of in sweeping, add citric acid and gallic acid (quality proportioning is 4:1) as combined depressant 0.5kg/t raw ore, sweep two operations and add sulfuric acid 3.0kg/t raw ore, the grade obtaining concentrate is 26.63%, the rate of recovery 80.15%, productive rate is the mineral processing index of 53.3%.
Embodiment 4:
Haikou phosphorus ore, ore main mineral constituent is collophane, secondary to a small amount of crystallite apatite, secondary mineralogical composition based on dolomite, containing quartz, calcite, feldspar, calcedony and a small amount of tourmaline, glauconite, muscovite and carbon shale thing etc.Ore main chemical compositions has P
2o
5﹑ CaO ﹑ SiO
2, be secondly CO
2﹑ MgO
2and Fe
2o
3﹑ Al
2o
3 ﹑﹑ F etc., ore industrial type is silicon calcium quality phosphorus block rock.
For phosphorus ore bi-anti-symmetric matrix test low in Yunnan Haikou, raw ore passes through crusher in crushing, ore grinding is carried out again by ore mill, mog is-0.074mm92.67%, add water and size mixing to concentration 20-50%, reverse flotation is roughly selected and for roughly selecting de-magging is: sulfuric acid dosage is 9kg/t raw ore, citric acid and tannic acid (quality proportioning 5:1) consumption 1kg/t raw ore, fatty acid anion collecting agent TSM-2 consumption 0.9kg/t raw ore; Selected de-magging is: sulfuric acid 1kg/t raw ore, fatty acid anion collecting agent TSM-20.3kg/t raw ore; Desiliconization process: amine cation type collecting agent cocodiamine 0.6kg/t raw ore, defoamer 100g/t raw ore.After regime of agent is determined, be determined by experiment best open circuit flow process be de-magging is one roughing, primary cleaning and once purging selection; Desiliconization is one roughing and once purging selection.Finally obtain concentrate grade 31.11%, the rate of recovery reaches 79.95%, and ore dressing productive rate is the mineral processing index of 54.96%.
Claims (1)
1. a phosphate reverse flotation technique, it is characterized in that including following steps: rock phosphate in powder is entered reverse floatation process by muck, ore grinding with after sizing mixing, wherein, sulfuric acid or phosphoric acid is added in gained ore pulp as adjusting agent and inhibitor after sizing mixing, add small molecular organic acid again as combined depressant, suppress phosphate mineral, adopt fatty acid or fatty acid soaps class collecting agent, carry out reverse flotation and deviate from carbonate mineral, obtain high-grade low magnesium phosphorus concentrate, described reverse floatation process is direct reverse flotation technique, single reverse floatation process or bi-anti-symmetric matrix technique, to deviate from carbonate mineral, reduce the content of MgO, described interpolation sulfuric acid or phosphoric acid are to adjust the pH value 4-6 of ore pulp, the consumption of described fatty acid or fatty acid soaps class collecting agent is 0.3 ~ 2.0kg/t rock phosphate in powder, described small molecular organic acid is citric acid, succinic acid, malic acid, the mixture of any two kinds of gallic acid and tannic acid, its consumption in reverse floatation process is 0.5kg/t ~ 3.0kg/t rock phosphate in powder.
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|---|---|---|---|---|
| CN103706488A (en) * | 2013-12-31 | 2014-04-09 | 中蓝连海设计研究院 | Reverse flotation technology of phosphate ore in alkaline medium |
| CN103909017B (en) * | 2014-04-18 | 2017-02-15 | 武汉工程大学 | Flotation process for silicon-calcium mixed collophanite containing organic carbon |
| CN104259013A (en) * | 2014-08-08 | 2015-01-07 | 西北矿冶研究院 | Inhibitor for separating blue chalcocite from pyrite and beneficiation method thereof |
| CN104437819B (en) * | 2014-11-04 | 2017-05-31 | 中蓝连海设计研究院 | A kind of suspension and method for improving phosphate reverse flotation carbonate efficiency |
| CN104787739A (en) * | 2014-12-10 | 2015-07-22 | 湖北新洋丰肥业股份有限公司 | Powdered monoammonium phosphate with 60% of total nutrient and production method |
| CN104624379B (en) * | 2014-12-29 | 2017-07-18 | 中蓝连海设计研究院 | A kind of positive and negative reverse flotation method of low-grade silicon calcium collophanite |
| CN104741244B (en) * | 2015-04-23 | 2017-04-12 | 中国地质科学院矿产综合利用研究所 | Silicon-calcium collophanite normal-temperature direct flotation collecting agent and preparation method thereof |
| CN104826741B (en) * | 2015-05-08 | 2017-05-31 | 中蓝连海设计研究院 | A kind of flotation and water return method for collophane bi-anti-symmetric matrix technique |
| CN104907183B (en) * | 2015-07-03 | 2017-12-12 | 武汉工程大学 | A kind of silico-calcium matter low grade collophanite direct reverse flotation technique |
| CN105152716B (en) * | 2015-09-05 | 2018-05-08 | 山东红日阿康化工股份有限公司 | A kind for the treatment of process of the acid solution produced in phosphorus ore acid system ore dressing and ore dressing process and application |
| CN105268560A (en) * | 2015-11-13 | 2016-01-27 | 中蓝连海设计研究院 | Method for simultaneous anti-flotation of carbonate and silicate in phosphorus ore |
| CN105562213A (en) * | 2015-12-23 | 2016-05-11 | 中蓝连海设计研究院 | Preparation method for phosphorus ore reverse flotation depressing agent sulfuric acid and reverse flotation method |
| CN105728177A (en) * | 2016-03-10 | 2016-07-06 | 湖北大峪口化工有限责任公司 | Leaching-reverse flotation method of collophanite |
| CN105833986B (en) * | 2016-05-23 | 2019-03-08 | 武汉工程大学 | A kind of manganese matter low-grade phosphate ore demanganize direct reverse flotation technique |
| CN107159468A (en) * | 2017-04-20 | 2017-09-15 | 宜昌东圣磷复肥有限责任公司 | A kind of low grade collophanite reverse floatation process |
| CN108940601B (en) * | 2017-05-24 | 2022-03-18 | 中蓝连海设计研究院有限公司 | Application and use method of aminodisuccinic acid or iminodisuccinic acid salt |
| CN110612161B (en) * | 2017-05-30 | 2022-07-01 | 埃科莱布美国股份有限公司 | Improved composition and process for reverse froth flotation of phosphate ores |
| CN107890955A (en) * | 2017-11-06 | 2018-04-10 | 云南磷化集团有限公司 | A kind of and supporting short route method for floating of chemical plant installations |
| CN108620240B (en) * | 2018-05-22 | 2019-10-08 | 中南大学 | A kind of sulfide mineral inhibitor of bismuth and its application |
| CN110280392A (en) * | 2019-07-15 | 2019-09-27 | 宜都兴发化工有限公司 | A kind of preparation method of vegetable fatty acid galla turcica ester collecting agent |
| CN110394239A (en) * | 2019-08-26 | 2019-11-01 | 贵州大学 | A kind of method for floating of Sedimentary Calcareous phosphorite |
| CN111036412B (en) * | 2019-11-27 | 2021-03-16 | 东北大学 | Application of inhibitor HPMA in positive flotation and magnesium removal of phosphate ore |
| CN111451001B (en) * | 2020-03-10 | 2021-05-11 | 中国地质科学院矿产综合利用研究所 | Medium-low grade mixed collophanite flotation separation reagent system and application thereof |
| CN112705360A (en) * | 2020-12-11 | 2021-04-27 | 山东省地质科学研究院 | Oleic acid flotation process method of tourmaline ore |
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| CN115400881A (en) * | 2022-08-26 | 2022-11-29 | 广东邦普循环科技有限公司 | Method for purifying and whitening phosphogypsum |
| CN115594353B (en) * | 2022-10-28 | 2024-06-04 | 矿冶科技集团有限公司 | Treatment method of collophanite double reverse flotation wastewater |
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